WO2002053672A1

WO2002053672A1 - Derived timber products consisting of wood parts glued by means of polyisocyanates

Info

Publication number: WO2002053672A1
Application number: PCT/EP2002/000012
Authority: WO
Inventors: Karl Häberle; Marcus Leubner; Eberhard PFÜTZE; Michael Schmidt
Original assignee: Basf Aktiengesellschaft
Priority date: 2001-01-04
Filing date: 2002-01-03
Publication date: 2002-07-11
Also published as: US20040071981A1; NO20033056D0; DE10100220A1; NO20033056L; NZ526742A; AU2002229693B2; CA2433055A1; EP1349901A1

Abstract

The invention relates to derived timber products consisting of wood parts which are glued by means of an adhesive composition, and such adhesive compositions. Said adhesive composition contains a prepolymer (prepolymer P) carrying isocyanate groups and derived from (A) a constituent A containing (A1) between 25 and 100 wt. % of a triglyceride having a plurality of reactive groups which can react with isocyanate groups in an addition reaction (triglycerides A1), and (A2) between 0 and 75 wt. % of another compound having at least one reactive group which can react with isocyanate groups in an addition reaction (constituent A2); and (B) a constituent B containing a polyisocyanate, optionally standard auxiliary and addition agents, optionally an activator, and optionally a filler material.

Description

Wood materials from wooden parts glued with polyisocyanates

description

The invention relates to wood-based materials made from wooden parts containing an adhesive composition

an isocyanate group-bearing prepolymer (prepolymer P), derived from

A) containing a component A.

AI) 25 to 100 wt .-% of a triglyceride with several reactive groups with isocyanate groups in one

Can react addition reaction (triglycerides AI), and

A2) 0 to 75% by weight of another compound having one or more reactive groups which can react with isocyanate groups in an addition reaction (component A2), and

B) a component B containing a polyisocyanate,

where appropriate, customary auxiliaries and additives

optionally an activator and

- optionally a filler,

are glued.

The invention further relates to adhesive compositions for this area of application.

Adhesive compositions for the production of wood-based materials such as plywood, blockboard, continuous board and glulam are subject to special requirements, which affect the processability of the adhesive compositions and the

Usage properties of the derived timber products concerned.

As far as the processing properties are concerned, the adhesive compositions of the prior art are considered to be in need of improvement, particularly with regard to their storage stability and viscosity. A lower one is desired Viscosity, so that the adhesive compositions can be transferred and conveyed more easily, for example by pumping, and distributed on the surfaces to be bonded.

In terms of the properties of use, the focus is on the need for the wood-based materials a) not to emit pollutants such as formaldehyde and b) to be as resilient as possible. The latter is of particular importance for glulam, as it is known that it is used in the form of beams or beams for components in buildings or ships.

While the mechanical load-bearing capacity of wood-based materials stored in dry conditions is generally completely satisfactory, that of wood-based materials that have been dried or that have been dried after wet storage is still considered to be in need of improvement.

The importance of these properties is particularly evident in the fact that these parameters are officially checked and that the wood-based materials are only officially approved if they meet certain minimum requirements.

DE-A-4 412 759 discloses a formaldehyde-free, filler-containing adhesive composition based on an isocyanate-containing polyurethane prepolymer. This adhesive composition has, in particular, a viscosity which is not very suitable for processing and uncompromising pressing times. The viscosity is particularly important for the pumpability and the ability of the adhesive composition to penetrate the substrate to be bonded (adhesion).

Furthermore, polyisocyanate-containing adhesive compositions are described in the earlier documents EP-A-1 072 620 and EP-A-1 072 621 and in EP application No. 01 123 829.2.

The task was therefore to provide adhesive compositions with good processing properties that can be further processed into wood-based materials with a good application-technical profile, in particular a high mechanical strength of moisture-stored wood-based materials is required.

Accordingly, the wood-based materials defined at the outset and the adhesive compositions were found.

In general, the adhesive compositions from which the wood-based materials according to the invention are made contain up to 99.99% by weight, preferably 70 to 99.9% by weight of the prepolymer (P)

0 to 10% by weight, preferably 0.001 to 10% by weight, particularly preferably 0.1 to 2% by weight of an activator - 0 to 20% by weight, preferably 0 to 10% by weight, particularly preferably 0% by weight of a filler and

0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 5% by weight of a customary auxiliary or additive.

Particularly preferred adhesive compositions contain practically no effective amounts of filler and consist essentially of

up to 99.99% by weight, preferably 80 to 99.9% by weight of the prepolymer P

0.001 to 10 wt .-%, preferably 0.1 to 2 wt .-% of an activator and

0 to 20 wt .-%, preferably 0 to 10 wt .-% of an auxiliary or additive.

If the adhesive compositions contain effective amounts of filler, these preferably consist essentially of

up to 99.99% by weight, preferably 70 to 99.9% by weight of the prepolymer P

0.001 to 10 wt .-%, preferably 0.1 to 2 wt .-% of an activator and

0.1 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 1 to 5% by weight of an auxiliary or additive.

The wood-based materials according to the invention, in particular plywood, plywood board, continuous wood board or plywood board, can be produced with the aforementioned adhesive compositions using the same methods by which the wooden parts from which they are composed are otherwise processed together with the otherwise customary aminoplast or phenoplast resins.

In particular, glulam or continuous wood planks are made from wooden boards by finger jointing the narrow edges. In the same way one proceeds with advantage in the production of endless wood board.

The method of finger jointing is generally known and is described below using the example of finger jointing carried out according to DIN 68140 Part 1. In the production of glulam, several layers of finger-glued wooden boards are generally connected to one another by gluing the side surfaces of the wooden boards with the adhesive compositions according to the invention.

The use of low-filler or essentially filler-free adhesive compositions has proven to be advantageous in the manufacture of wood-based materials and in particular in finger jointing.

Filler-containing adhesive compositions are more difficult to process because, with low-viscosity settings, the suspended filler settles after a short time and has to be stirred up immediately before processing. The suspensions are stable at highly viscous settings, but are less preferred for the reasons mentioned above.

Filler-containing adhesive compositions are particularly disadvantageous when mechanically bonding surfaces that have narrow and deep incisions. Such a surface can be found, for example, in finger jointing in accordance with DIN 68140 Part 1. Here, the tines are usually designed in their cross-section as pointed triangles, so that an equally pointed, triangular incision is formed by one leg of two adjacent tines. A tool combing through the incisions is generally used to apply an adhesive composition to the leg surfaces of the tines, the shape of the adhesive-applying area of which is adapted to the incisions. In general, the adhesive composition is applied from the flanks of this application chamber, which usually have approximately the same length as the legs, by means of slots arranged in this area.

In the case of filler-containing adhesive compositions, these slots have to be cleaned frequently in order to avoid blockages and the resulting fluctuations in quality.

Filler-containing adhesive compositions are therefore used above all when the surfaces of the wooden parts to be glued have unevenness and the adhesive joints have a thickness of 0.1 to 1 mm, as is the case especially with surface gluing. For finger jointing these are therefore only considered in two lines. Here the thickness of the joint is generally 0.05 to 0.2, preferably 0.09 to 0.13 mm. The adhesive compositions according to the invention preferably contain those prepolymers P which have an NCO content of 5 to 30, preferably 10 to 20, particularly preferably 13 to 17% by weight. Its viscosity at 25 ° C is 300 to 45000, preferably 5 500 to 25000 mPas.

To prepare the prepolymer P, components A and B are generally used in proportions such that the ratio of the reactive groups which react with isocyanate groups in an addition reaction to the isocyanate groups is 0.05: 1 to 0.8: 1, preferably 0 , 1: 1 to 0.5: 1.

Components A and B are reacted in the stated proportions in a generally known manner in accordance with the desired 5 NCO content of the prepolymers P.

Components A preferably contain 75 to 100%, particularly preferably essentially exclusively, a triglyceride Al.

0 Triglycerides AI are understood to mean esters of glycerol which have at least two reactive groups which can react with isocyanate groups in an addition reaction. They are e.g. selected from the group consisting of primary amino groups, secondary amino groups, alcoholic hydroxyl groups and 5 mercapto groups.

These compounds can be of natural, synthetic or semi-synthetic origin. The natural triglycerides are to be understood as esters of carboxylic acids bearing hydroxyl groups, such as castor oil.

Semi-synthetic triglycerides are compounds that are obtained by chemical modification of natural triglycerides. These are, for example, compounds that can be prepared by epoxidation and subsequent hydro-, glyco- and / or aminolysis of olefinically unsaturated natural triglycerides. Such compounds are sold, for example, by Harburger Fettchemie Brinckmann & Mergeil GmbH under the name Merginat ^® .

Of course, synthetic triglycerides can also be used, e.g. can be obtained by esterifying glycerol with appropriately substituted carboxylic acids.

Natural and partially synthetic triglycerides 5 are preferably used, particularly preferably natural, very particularly preferably castor oil. Component A2 in particular comes into consideration those which are referred to in EP-A-1 072 620 as "component A".

Usually these are compounds with one or more reactive groups that can react with isocyanate groups in an addition reaction. They are e.g. selected from the group consisting of primary amino groups, secondary amino groups, alcoholic hydroxyl group and mercapto groups.

Component A2 includes polyhydric alcohols with a molecular weight of less than 400 g / mol, such as short-chain aliphatic diols with 2 to 14 carbon atoms, e.g. 1, 4-butanediol or 1,6 hexanediol, preferred.

So-called macropolyols, ie polyhydric alcohols with a molecular weight of 400 to 10,000, which contain ester or ether groups as repeating units, are less preferred.

Components A2 can also be, at least in part, those which can react with isocyanate groups to form urea groups, ie compounds with primary or secondary amino groups and water. If a filler is used, the water can also be contained in the filler, as described in the earlier EP application No. 01 123 829.2.

For component B, which preferably contains a polyisocyanate, the isocyanates which are customarily used are the aliphatic, cycloaliphatic, araliphatic or aromatic isocyanates known per se, preferably di- or triisocyanates. Suitable isocyanates are also in the

EP-A-1 072 620 described as "component B". 4, 4 '-2, 4' or 2, 2 '-diphenylmethane diisocyanate or mixtures thereof (MDI) are preferred.

Well-known compounds which accelerate the reaction of isocyanate groups and the reactive groups which can react with isocyanate groups in an addition reaction can be used as activators. For the purposes of the invention, reactive groups which can react with isocyanate groups in an addition reaction are, above all, alcoholic hydroxyl groups, primary and secondary amino groups and mercaptans, and the hydroxyl group of water. Carboxylic acid groups are not included. Such activators are generally known in polyurethane chemistry and are listed, for example, in EP-A-1 072 620 as "catalysts". Tertiary amines such as dimethylmorpholine are preferred.

As auxiliaries and additives, adhesive compositions contain customary additives such as surface-active substances, stabilizers, dyes, pigments, flame retardants, fungistatic and bacteriostatic substances and solvents.

Customary auxiliaries and additives, which are preferred, can also be found under this name and under the name solvent in EP-A-1 072 620.

In addition to the fibrous fillers mentioned in EP-A-1 072 621, the following fillers are used, e.g. Polyamide fibers, usual particulate fillers into consideration.

In general, the particulate fillers are customary inorganic fillers, such as kaolin or other aluminosilicates, or customary organic fillers, such as wood flour.

The incorporation of the activators, auxiliaries and additives as well as the fillers is not critical and can be carried out using customary methods.

The wood-based materials according to the invention are used in particular in building construction, civil engineering, shipbuilding, vehicle construction and aircraft construction.

The following examples are intended to explain the invention in more detail.

example 1

500 g of a 50/50 mixture of 2,4- and 4,4'-diphenylmethane diisocyanate were placed in a stirred kettle and heated to 80 ° C. with stirring. For this purpose, 345 g castor oil (with the OH number 160 mg KOH / g) were slowly added.

After the addition had ended, the mixture was stirred for 60 minutes, cooled to 25 ° C. and filled.

The product had an NCO content of 14.3% by weight and a viscosity of 7200 mPas at 25 ° C. Example 2 (comparison)

The procedure was as described in Example 3 of EP-A-1 072 620. 5

Exam :

99.2 parts of the adhesives from Examples 1 and 2 were mixed with 0.8 parts of 2.2 ^λ -dimorpholinodiethyl ether and glued in accordance with the specification of DIN EN 302, Part 1.

The tensile shear test gave the following results:

Tensile shear test according to DIN EN 302, part 1 5

0 0.3 mm joint is not included in DIN EN 301, requirement corresponds to 0.5 mm joint.

Treatment AI: 7 days storage in normal climate

(20 ± 2 ° C; 65 ± 5% relative humidity) 5

Treatment A4: 7 days storage in normal climate

(20 ± 2 ° C; 65 ± 5% relative air humidity), then submerged in boiling water for 6 h, then submerged in water at 15 ° C for 5 h; Test specimen tested in wet condition

Treatment A5: 7 days storage in normal climate

(20 ± 2 ° C; 65 ± 5% relative air humidity), then submerged in boiling water for 6 h, then submerged in water at 15 i for 2 h 5 ° C, then 7 days drying in normal climate (20 ± 2 ° C; 65 ± 5% relative air humidity); Test specimen tested in dry condition

10

15

20

25

30

35

40

45

Claims

claims

1. Wood-based materials from wooden parts, containing an adhesive composition

an isocyanate group-bearing prepolymer (prepolymer P) derived from

A) containing a component A.

AI) 25 to 100 wt .-% of a triglyceride with several reactive groups that can react with isocyanate groups in an addition reaction (triglycerides AI), and

B) a component B containing a polyisocyanate,

where appropriate, customary auxiliaries and additives,

optionally an activator and

optionally a filler,

are glued.

2. Wood-based materials according to claim 1, wherein it is glulam, endless wood board, plywood or blockboard.

3. Glulam or endless wood board according to claim 2

Wooden boards with the narrow edges glued together.

4. Glulam according to claim 2 or 3, wherein the side surfaces of the boards are glued with an adhesive composition according to claim 1.

5. Glulam according to claim 3 or 4, wherein the adhesive composition is substantially free of filler.

6. Wood-based materials according to claims 1 to 5, wherein the reactive groups of the triglycerides AI which can react with isocyanate groups in an addition reaction are selected from the group consisting of primary amino groups, secondary amino groups, alcoholic hydroxyl groups and mercapto groups ,

7. Wood-based materials according to claim 6, wherein the triglycerides AI are derived from hydroxycarboxylic acids.

8. Wood-based materials according to claim 7, wherein the triglycerides AI are castor oil.

9. Wood-based materials according to claims 1 to 8, wherein polyols with a molecular weight of less than 400 g / mol are mainly used as component A2.

10. Adhesive composition consisting essentially of

- Up to 99.99 wt .-% of an isocyanate-bearing prepolymer (prepolymer P), derived from

A) containing a component A.

A2) 0 to 75% by weight of another compound having one or more reactive groups which can react with isocyanate groups in an addition reaction (component A2),

B) a component B containing a polyisocyanate,

0 to 20% by weight of conventional auxiliaries and additives,

0 to 10 wt .-% of an activator and

0 to 20% by weight of a filler.

11. Adhesive composition consisting essentially of

- Up to 99.99 wt .-% of an isocyanate-bearing prepolymer (prepolymer P), derived from A) containing a component A.

AI) 25 to 100 wt .-% of a triglyceride with several reactive groups that can react with isocyanate groups in an addition reaction

(Triglyceride AI), and

B) a component B containing a polyisocyanate,

0 to 20% by weight of auxiliaries and additives and

0.001 to 10% by weight of an activator.

Wood materials from wooden parts glued with polyisocyanates

composition

Wood-based materials from wooden parts containing an adhesive composition

an isocyanate group-bearing prepolymer (prepolymer P), derived from

A) containing a component A.

Can react addition reaction (triglycerides AI), and

B) a component B containing a polyisocyanate,

where appropriate, customary auxiliaries and additives,

optionally an activator and

- optionally a filler,

are glued, as well as adhesive compositions.